环氧丁烷尾气溶剂吸收及精制工艺

doi:10.11949/0438-1157.20221564

摘要/Abstract

摘要：

针对以过氧化氢乙苯法生产1，2-环氧丁烷（简称环氧丁烷）工艺中环氧丁烷尾气难回收问题，提出了以环氧丁烷精制单元萃取剂正辛烷为吸收剂和利用精制单元萃取精馏塔同时作为解吸塔的环氧丁烷回收新工艺。该工艺同时考虑无催化环氧丁烷水解生成1，2-丁二醇，利用1，2-丁二醇与正辛烷可形成最低温度非均相共沸物特性，侧线采出共沸物脱除1，2-丁二醇达到纯化循环萃取剂提高萃取效率的分离目标。选用NRTL热力学方法，对上述流程进行了全流程模拟和优化设计，分析了溶剂比、理论塔板数、吸收剂进料温度等主要工艺参数对分离的影响规律。结果表明：新工艺对环氧丁烷回收率达到99.99%（质量），对环氧丁烷工业装置产能提升、节能降耗和挥发性有机物（VOCs）治理具有实际应用价值。

关键词: 过氧化氢乙苯法, 环氧丁烷, 吸收, 萃取精馏

Abstract:

In view of the difficulty of recovering 1,2-butylene oxide (BO) contained in tail gas in ethylbenzene hydroperoxide 1,2-butylene oxide (EBHP) plant, a novel absorption process for BO recovery with extraction solvent and extractive distillation (as desorption column) was proposed in this work, in that the reaction of both BO non-catalyzed hydrolysis reaction was considered. Meanwhile, the separation efficiency affected from solvent was characterized and solved based on the characteristics of liquid-liquid split for 1,2-butylene glycol (12BDO) and extraction solvent mixture at certain condition. The simulation and design optimization for the full process using Aspen Plus package with NRTL thermodynamic model were carried out. The influence of the main technological parameters, such as solvent ratio, the number of theoretical plates and the feed temperature of solvent was discussed. The results show that the new process has a recovery rate of 99.99% (mass) for butylene oxide, which has practical application value for the production capacity improvement of butylene oxide industrial equipment, energy saving and consumption reduction, and volatile organic compounds (VOCs) treatment.

Key words: ethylbenzene hydroperoxide process, 1,2-butylene oxide, absorption, extractive distillation

中图分类号:

TQ 028.8

李木金, 胡松, 施德磐, 赵鹏, 高瑞, 李进龙. 环氧丁烷尾气溶剂吸收及精制工艺[J]. 化工学报, 2023, 74(4): 1607-1618.

Mujin LI, Song HU, Depan SHI, Peng ZHAO, Rui GAO, Jinlong LI. A process for offgas absorption and purification of 1,2-butylene oxide[J]. CIESC Journal, 2023, 74(4): 1607-1618.

图/表 20

表1 不同组分在各溶剂中的亨利系数

Table 1 Henry coefficients of different solutes in various solutions

Solvent	Henry coefficient/mmHg^①
Solvent	BO	Acetone	Water	N₂
n-octane (nC₈)	126.30	312.83	882006.0	50533.4
iso-octane (isoC₈)	129.43	303.59	795399.4	56078.6
2-methyl heptane (methylC₇)	125.76	307.30	851851.3	51586.9
cumene	76.18	123.74	151607.6	60638.9
ethyle benzene (ethylB)	76.96	123.94	148667.1	65146.4

图1 C8溶剂对丙酮/BO及水/BO相对挥发度的影响

Fig.1 Effects of C8 solvent on the relative volatility for acetone/BO and water/BO mixtures

图2 nC8萃取剂中12BDO浓度对丙酮/BO相对挥发度的影响

Fig.2 Effect of 12BDO concentration in nC8 solvent on relative volatility for acetone/BO

表2 12BDO与nC8二元共沸体系组成及共沸温度

Table 2 Azeotropic temperature and mass composition for 12BDO-nC8

Item	12BDO/%(mass)	nC₈/%(mass)	Azeotropic temperature/℃
UNIQUAC-UNIFAC	5.08	94.92	123.51
NRTL-UNIFAC	4.94	95.06	123.6
COSMO-SAC	2.91	97.09	124.5

图3 BO-12BDO-nC8残留曲线

Fig.3 Distillation residue curves of BO-12BDO-nC8 ternary system

图4 环氧丁烷尾气回收及溶剂纯化工艺流程简图

Fig.4 Flowsheet of BO offgas recovery and BO purification process

图5 BO+丙酮、BO+12BDO和12BDO+nC8二元气液(液)相图比较

Fig.5 VL(L)E for binary mixtures of BO(1)+ acetone(2), BO(1)+12BDO(2), and 12BDO(1)+nC8(2) at 101.32 kPa

图6 OAC溶剂比对吸收过程的影响

Fig.6 Effect of the mass ratio of absorbent to offgas for OAC on the absorption process

图7 吸收剂温度对吸收过程的影响

Fig.7 Effect of the absorbent temperature on the absorption process

图8 OAC理论级数对吸收过程的影响

Fig.8 Effect of the number of theoretical stages for OAC on absorption process

图9 EDC溶剂比对分离过程的影响

Fig.9 Effect of the solvent mass ratio for EDC on the separation process

图10 EDC理论塔板数对分离过程的影响

Fig.10 Effect of the number of theoretical stages for EDC on the separation process

图11 馏出率对产品和再沸器能耗的影响

Fig.11 Effect of distillation rate on product and reboiler heat duty

图12 萃取剂和粗BO进料位置对分离过程的影响

Fig.12 Effect of feed stage of solvent and crude BO on the separation process

图13 萃取剂的温度对分离过程的影响

Fig.13 Effect of temperature of solvent on the separation process

图14 SRC理论级数、进料位置、塔顶馏出率以及回流比对分离过程的影响

Fig.14 Effect of the number of theoretical stage, feed stage, distillation rate and refiux ratio for SRC on the separation process

图15 侧线采出位置、采出量以及回流位置对12BDO分离的影响

Fig.15 Effect of stage of side line production, mass flow and stage of side reflux on separation of 12BDO

表3 流程模拟优化工艺条件

Table 3 Optimization parameters for flowsheet simulation

Unit Block	Parameter	Value
offgas absorption column (OAC)	operating pressure/kPa	400
	operating temperature/℃	20.0
	theoretical stage	9
	feed stage of BO offgas	9
	temperature of solvent/℃	20
	solvent ratio	1.5
extractive distillation column (EDC)	operating pressure/kPa	141
	theoretical stage	50
	feed stage of solvent	1
	feed stage of crude BO	7
	mass solvent ratio	2.3
	distillation rate/(kg/h)	3000
solvent recovery column (SRC)	operating pressure/kPa	121
	theoretical stage	31
	feed stage of feeding	9
	mass reflux ratio	2.7
	distillation rate/(kg/h)	12490
	stage of side line production	28
	mass flow of side line production/(kg/h)	550
	stage of side reflux	30

图16 吸收塔、萃取精馏塔和溶剂回收塔温度和关键组分分布

Fig.16 Profiles of temperature and key components in OAC, EDC and SRC

图17 全流程物料平衡图（图中F为质量流量，kg/h；质量组成单位为%）

Fig.17 Balance diagram of mass flow for all key components

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